CN115873309B - Inorganic nano-based composite flame retardant, preparation method thereof and application thereof in wood-plastic composite material - Google Patents
Inorganic nano-based composite flame retardant, preparation method thereof and application thereof in wood-plastic composite material Download PDFInfo
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- CN115873309B CN115873309B CN202211459420.7A CN202211459420A CN115873309B CN 115873309 B CN115873309 B CN 115873309B CN 202211459420 A CN202211459420 A CN 202211459420A CN 115873309 B CN115873309 B CN 115873309B
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- 239000000463 material Substances 0.000 title claims abstract description 95
- 239000003063 flame retardant Substances 0.000 title claims abstract description 89
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- 229920001587 Wood-plastic composite Polymers 0.000 title claims abstract description 55
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- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 80
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 77
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- 238000006243 chemical reaction Methods 0.000 claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 17
- 239000000017 hydrogel Substances 0.000 claims description 16
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 15
- 239000012760 heat stabilizer Substances 0.000 claims description 15
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- 238000001354 calcination Methods 0.000 claims description 12
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001338 self-assembly Methods 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
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- 239000004609 Impact Modifier Substances 0.000 claims description 7
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- 229910052751 metal Inorganic materials 0.000 claims description 7
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- 150000001868 cobalt Chemical class 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
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- 238000012545 processing Methods 0.000 claims description 4
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- 239000011425 bamboo Substances 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims 1
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- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 3
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- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an inorganic nano-based composite flame retardant, a preparation method thereof and application thereof in wood-plastic composite materials. The inorganic nano-based composite flame retardant comprises a transition metal nano-oxide, two-dimensional montmorillonite nano-sheets and a metal organic framework material; the transition metal nano-oxide is loaded on the surface of the two-dimensional montmorillonite nano-sheet to form the two-dimensional montmorillonite nano-sheet loaded with the transition metal nano-oxide; the metal organic framework material is coated on the surface of the two-dimensional montmorillonite nano-sheet loaded with the transition metal nano-oxide to form a coating layer. Modifying the two-dimensional montmorillonite nano-sheets loaded with the transition metal nano-oxides by utilizing the surface coating layer so as to improve the compatibility of the inorganic nano-based composite flame retardant and the PVC-based wood-plastic composite material; solves the defects of large addition amount of flame retardant, low flame retardant and smoke suppression efficiency, and reduced mechanical property and decorative effect of the traditional flame retardant PVC-based wood-plastic composite material.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to an inorganic nano-based composite flame retardant, a preparation method thereof and application thereof in wood-plastic composite materials.
Background
The wood-plastic composite material is a novel composite material which is prepared by taking wood fiber materials in the forms of fiber, powder and the like as filling or reinforcing materials, taking thermoplastic plastics as matrix materials, adding various auxiliary agents and compounding by various processing means such as extrusion, hot pressing, mould pressing or injection molding. Common thermoplastic matrices include Polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), and the like.
In recent years, PVC-based wood-plastic composite materials have better appearance effects, and are widely applied to the fields of building doors and windows, interior decoration, furniture and the like. In these applications, the fire resistance of the material is an important factor in ensuring safe use of the material. Although PVC has good flame retardance, the addition of a large amount of wood powder and low-molecular auxiliary agents makes the PVC-based wood-plastic composite material easy to ignite, and simultaneously a large amount of concentrated smoke and toxic gas are emitted during combustion. In order to improve the flame retardant and smoke suppression properties of PVC-based wood-plastic composites, it is often necessary to add flame retardants in the preparation of such composites.
The flame retardants commonly used at present are halogen-containing flame retardants and halogen-free flame retardants, wherein inorganic flame retardants are typical of the halogen-free flame retardants, and have the greatest advantages of no generation of toxic and corrosive gases and environmental friendliness. The disadvantage is that the filling amount is large, the compatibility with the polymer matrix is poor, and the mechanical property and the processing property of the polymer matrix are damaged. Therefore, a flame-retardant system suitable for the PVC-based wood-plastic composite material is developed, the interface compatibility between the flame-retardant system and the PVC-based wood-plastic composite material is improved, the mechanical property of the PVC-based wood-plastic composite material is ensured, and the improvement of the flame-retardant property is the key point of future research. Therefore, flame retardants which are halogen-free, low in toxicity, low in smoke, high in heat resistance and good in compatibility with a matrix have gradually become the development direction of flame retardant materials in the future.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides an inorganic nano-based composite flame retardant, a preparation method thereof and application thereof in wood-plastic composite materials. The inorganic nano-based composite flame retardant comprises a transition metal nano-oxide, two-dimensional montmorillonite nano-sheets and a metal organic framework material; the transition metal nano-oxide is loaded on the surface of the two-dimensional montmorillonite nano-sheet to form the two-dimensional montmorillonite nano-sheet loaded with the transition metal nano-oxide; the metal organic framework material is coated on the surface of the two-dimensional montmorillonite nano-sheet loaded with the transition metal nano-oxide to form a coating layer. Modifying the two-dimensional montmorillonite nano-sheets loaded with the transition metal nano-oxides by utilizing the surface coating layer so as to improve the compatibility of the inorganic nano-based composite flame retardant and the PVC-based wood-plastic composite material; solves the defects of large addition amount of flame retardant, low flame retardant and smoke suppression efficiency, and reduced mechanical property and decorative effect of the traditional flame retardant PVC-based wood-plastic composite material.
The invention aims at realizing the following technical scheme:
an inorganic nano-based composite flame retardant, wherein the inorganic nano-based composite flame retardant comprises a transition metal nano-oxide, a two-dimensional montmorillonite nano-sheet and a metal organic framework material; the transition metal nano-oxide is loaded on the surface of the two-dimensional montmorillonite nano-sheet to form the two-dimensional montmorillonite nano-sheet loaded with the transition metal nano-oxide; the metal organic framework material is coated on the surface of the two-dimensional montmorillonite nano-sheet loaded with the transition metal nano-oxide to form a coating layer.
According to an embodiment of the present invention, the transition metal nano-oxide is selected from at least one of nano-zinc oxide, nano-tin oxide, nano-chromium oxide, nano-iron oxide, nano-cobalt oxide, nano-nickel oxide, and nano-copper oxide.
According to an embodiment of the invention, the particle size of the transition metal nano-oxide is 20nm to 80nm, preferably 30nm to 60nm, for example 30nm, 40nm, 50nm or 60nm.
According to an embodiment of the invention, the average thickness of the two-dimensional montmorillonite nano-sheets is 10nm to 30nm, for example 10nm, 15nm, 20nm, 25nm or 30nm; the average length of the two-dimensional montmorillonite nano-sheets is 300 nm-500 nm, such as 300nm, 350nm, 400nm, 450nm or 500nm.
According to an embodiment of the invention, the metal organic framework material is selected from at least one of Zn-MOF, fe-MOF, cu-MOF, sn-MOF, co-MOF, ni-MOF and Cr-MOF.
According to an embodiment of the present invention, the organic ligand forming the metal organic framework material is selected from at least one of 2-amino terephthalic acid, dimethylimidazole, 2, 5-dihydroxyterephthalic acid, trimesic acid or terephthalic acid.
According to an embodiment of the invention, the transition metal salt forming the metal organic framework material is selected from at least one of zinc salt, tin salt, chromium salt, iron salt, cobalt salt, nickel salt and copper salt. Preferably at least one selected from zinc nitrate, tin chloride, chromium nitrate, iron nitrate, cobalt nitrate, nickel nitrate and copper nitrate.
According to an embodiment of the invention, the mass ratio of transition metal salt forming the metal organic framework material to organic ligand forming the metal organic framework material is 1 (2-4), for example 1:2, 1:3 or 1:4.
According to an embodiment of the invention, the mass ratio of the two-dimensional montmorillonite nano-platelets to the transition metal nano-oxide is (0.1-0.5): 1, for example 0.1:1, 0.2:1, 0.3:1, 0.4:1 or 0.5:1.
According to an embodiment of the invention, the average thickness of the coating layer is 3nm to 6nm, for example 3nm, 4nm, 5nm or 6nm.
According to an embodiment of the present invention, the metal organic framework material accounts for 0.5wt% to 3wt%, such as 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.2wt%, 1.4wt%, 1.5wt%, 1.8wt%, 2wt%, 2.2wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt% or 3wt% of the total mass of the inorganic nano-based composite flame retardant.
The invention also provides a preparation method of the inorganic nano-based composite flame retardant, which comprises the following steps:
(1) Mixing montmorillonite and sodium alginate to prepare a suspension;
(2) Dropwise adding the suspension in the step (1) into the aqueous solution of the first transition metal salt, and performing a crosslinking reaction to prepare hydrogel spheres;
(3) Drying the hydrogel spheres in the step (2) and calcining to prepare two-dimensional montmorillonite nano-sheets loaded with transition metal nano-oxides;
(4) Mixing the two-dimensional montmorillonite nano-sheets loaded with the transition metal nano-oxides, the second transition metal salt, the organic ligand and the organic solvent in the step (3), and performing self-assembly reaction to prepare the inorganic nano-based composite flame retardant.
According to an embodiment of the present invention, in the step (1), the montmorillonite has a lamellar structure, the average thickness of montmorillonite lamellar layers is 80nm to 120nm, and the average length of montmorillonite lamellar layers is 5 μm to 10 μm.
According to an embodiment of the invention, in step (1), the mass ratio of montmorillonite to sodium alginate is (0.01-0.1): 1, for example 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1 or 0.1:1.
According to an embodiment of the present invention, in the step (1), the method specifically includes the following steps:
adding montmorillonite into water, stirring, ultrasonic treating, adding sodium alginate, stirring to dissolve completely, and standing at room temperature for 12-24 hr to obtain uniform suspension.
Preferably, montmorillonite is added into deionized water and stirred and sonicated for 10-30min, then sodium alginate is added and stirred at 60-100 ℃ until completely dissolved, and then the mixture is left to stand at room temperature for 12-24 hours, thus obtaining a uniform suspension.
Preferably, the mass ratio of montmorillonite to water is (0.1-0.3): 100.
Preferably, after each 4-6 hours of standing in the standing process, the ultrasonic treatment is carried out for 1-2 hours, and then the standing and the ultrasonic treatment are carried out.
According to an embodiment of the present invention, in step (2), the first transition metal salt is selected from at least one of zinc salt, tin salt, chromium salt, iron salt, cobalt salt, nickel salt and copper salt. Preferably, the first transition metal salt is at least one selected from zinc nitrate, tin chloride, chromium nitrate, iron nitrate, cobalt nitrate, nickel nitrate, and copper nitrate.
According to an embodiment of the present invention, in the step (2), the aqueous solution of the first transition metal salt may include one transition metal salt or two or more transition metal salts.
According to an embodiment of the present invention, in step (2), the concentration of the transition metal salt in the aqueous solution of the first transition metal salt is 10 to 50g/L.
According to an embodiment of the present invention, in step (2), the mass ratio of the suspension to the aqueous solution of the first transition metal salt is (10-50): 100.
according to an embodiment of the present invention, in the step (2), the temperature of the crosslinking reaction is room temperature, and the time of the crosslinking reaction is 16 to 28 hours.
According to the embodiment of the invention, in the step (2), the hydrogel balls are washed for 2-5 times by adopting deionized water, and metal ions adsorbed on the surfaces of the hydrogel balls are removed.
According to an embodiment of the present invention, in the step (2), the hydrogel sphere has a diameter of 2mm to 5mm. The diameter of the hydrogel sphere can be controlled by controlling the size of the suspension liquid drops.
According to an embodiment of the present invention, in step (2), the first transition metal salt is used to form a transition metal nano-oxide supported on the surface of the two-dimensional montmorillonite nano-sheet.
According to an embodiment of the present invention, in step (3), the drying temperature is 50 to 100 ℃.
According to an embodiment of the present invention, in the step (3), the calcination is performed at a temperature of 400 to 800 ℃ (e.g., 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, or 800 ℃), the calcination is performed for a time of 2 to 6 hours (e.g., 2 hours, 3 hours, 4 hours, 5 hours, or 6 hours), and the calcination atmosphere is an air atmosphere.
According to an embodiment of the present invention, in step (4), the organic ligand is selected from at least one of 2-amino terephthalic acid, dimethylimidazole, 2, 5-dihydroxyterephthalic acid, trimesic acid and terephthalic acid.
According to an embodiment of the present invention, in step (4), the organic solvent is selected from at least one of methanol, ethanol, formaldehyde, acetaldehyde, DMF, and deionized water.
According to an embodiment of the present invention, in step (4), the second transition metal salt is selected from at least one of zinc salt, tin salt, chromium salt, iron salt, cobalt salt, nickel salt and copper salt. Preferably, the second transition metal salt is at least one selected from zinc nitrate, tin chloride, chromium nitrate, iron nitrate, cobalt nitrate, nickel nitrate, and copper nitrate.
According to an embodiment of the invention, in step (4), the mass ratio of the second transition metal salt to the organic ligand is 1 (2-4), for example 1:2, 1:3 or 1:4.
According to an embodiment of the invention, in step (4), the volume ratio of the sum of the masses of the second transition metal salt and the organic ligand to the organic solvent is (0.01-0.05) g:1mL, for example 0.01g:1mL, 0.02g:1mL, 0.03g:1mL, 0.04g:1mL or 0.05g:1mL.
According to an embodiment of the present invention, in the step (4), the mass ratio of the second transition metal salt to the transition metal nano oxide loaded two-dimensional montmorillonite nano sheet is 1 (5-15), for example, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14 or 1:15.
According to an embodiment of the present invention, in the step (4), the temperature of the self-assembly reaction is 25 ℃ to 80 ℃; the self-assembly reaction time is 6-24 h.
According to an embodiment of the present invention, in step (4), the self-assembly reaction is performed under stirring.
According to an embodiment of the present invention, in the step (4), after the self-assembly reaction is completed, a post-treatment step such as centrifugal washing and vacuum drying is further included. Preferably, the temperature of the vacuum drying is 60-100 ℃.
According to the embodiment of the invention, in the step (4), the second transition metal salt and the organic ligand can generate a metal organic framework material through self-assembly reaction, and the metal organic framework material is coated on the surface of the two-dimensional montmorillonite nano-sheet loaded with the transition metal nano-oxide.
According to an embodiment of the present invention, in the step (4), the metal element in the metal-organic framework material and the metal in the transition metal nano-oxide in the two-dimensional montmorillonite nano-sheet loaded with the transition metal nano-oxide may be the same or different.
The invention also provides the inorganic nano-based composite flame retardant prepared by the method.
The invention also provides application of the inorganic nano-based composite flame retardant in wood-plastic composite materials.
According to an embodiment of the invention, the wood-plastic composite is preferably a PVC-based wood-plastic composite.
The invention also provides a wood-plastic composite material, which comprises the inorganic nano-based composite flame retardant.
According to an embodiment of the invention, the wood-plastic composite further comprises a PVC resin.
According to an embodiment of the invention, the wood-plastic composite further comprises plant fiber powder, an impact modifier and a lubricant.
According to an embodiment of the invention, the wood-plastic composite further comprises a heat stabilizer.
According to the embodiment of the invention, the wood-plastic composite material comprises the following components in percentage by mass:
100 parts by mass of PVC resin;
30-60 parts of plant fiber powder; preferably 30, 35, 40, 45, 50, 55 or 60 parts by mass;
1-10 parts by mass of an inorganic nano-based composite flame retardant; preferably 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 parts by mass;
0-6 parts by mass of a heat stabilizer; preferably 0.5, 1, 2, 3, 4, 5 or 6 parts by mass;
2-4 parts by mass of an impact modifier; preferably 2, 2.5, 3, 3.5 or 4 parts by mass;
0.8-1.2 parts by mass of a lubricant; preferably 0.8, 0.9, 1, 1.1 or 1.2 parts by mass.
According to an embodiment of the present invention, the particle size of the plant fiber powder is 80 to 200 mesh.
According to an embodiment of the present invention, the plant fiber powder is at least one selected from poplar powder, bamboo powder, crop straw powder, and fruit shell powder.
According to an embodiment of the present invention, the heat stabilizer is selected from organic tin-based and metal soap-based heat stabilizers, for example, at least one of calcium zinc heat stabilizer, barium zinc heat stabilizer, potassium zinc heat stabilizer.
According to an embodiment of the present invention, the lubricant is at least one selected from stearic acid, stearate, paraffin wax, polyethylene wax; wherein the stearate is at least one selected from sodium stearate, potassium stearate, calcium stearate or zinc stearate.
According to an embodiment of the present invention, the impact modifier is selected from at least one of chlorinated polyethylene, polyacrylate, ethylene-vinyl acetate copolymer, methyl methacrylate-butadiene-styrene terpolymer.
According to the embodiment of the invention, the wood-plastic composite material is a flame-retardant smoke-suppressing PVC-based wood-plastic composite material.
The invention also provides a preparation method of the wood-plastic composite material, which comprises the following steps:
(a) Respectively weighing PVC resin, plant fiber powder, inorganic nano-based composite flame retardant, heat stabilizer, impact modifier and lubricant according to the parts by mass, and mixing to obtain materials;
(b) And (c) extruding the material obtained in the step (a) through a screw extruder for molding, and then performing hot pressing and curing to obtain the wood-plastic composite material.
According to an embodiment of the invention, in step (a), the mixing is performed in a high speed mixer.
According to an embodiment of the present invention, in step (b), the extrusion may be performed in a twin-screw extruder or in a single-screw extruder. The speed of the double-screw extruder is 20-30r/min, and the speed of the single-screw extruder is 5-8r/min.
According to an embodiment of the invention, in step (b), the temperature of the processing zone is 140 to 180℃and the die temperature is 150 to 170℃during extrusion. During extrusion, the extrusion temperature is kept below 200 ℃ to reduce thermal decomposition of plant fiber powder and PVC.
According to an embodiment of the present invention, in step (b), the hot pressing is performed at 155 to 175℃and 7MPa for 10 to 20 minutes using a hot press.
The invention has the beneficial effects that:
(1) The invention uses the negative-charged sodium alginate to weaken the interlayer acting force of the positive-charged montmorillonite, so that the montmorillonite layers gradually slip and peel off to prepare the two-dimensional montmorillonite nano-sheets, and simultaneously the carboxyl of the sodium alginate and positive ions on the two-dimensional montmorillonite nano-sheets are firmly combined together through electrostatic attraction; and then the cations of the sodium alginate are further substituted and crosslinked with transition metal ions to obtain hydrogel spheres, and finally carbon in the sodium alginate is removed by calcination to obtain the inorganic nano flame-retardant material with transition metal nano oxides loaded on the two-dimensional montmorillonite nano sheets, so that the problem that the two-dimensional montmorillonite nano sheets and the transition metal nano oxides are difficult to disperse is solved. On the basis, the surface of the two-dimensional montmorillonite nano-sheet loaded with the transition metal nano-oxide is coated with the metal organic framework material in situ to form the organic-inorganic hybrid material, so that the technical bottleneck that the inorganic nano flame-retardant material is easy to agglomerate and difficult to disperse in the organic polymer PVC matrix can be solved. The transition metal nano oxide and the two-dimensional montmorillonite nano plate have strong rigidity, and can improve the mechanical property of the polymer. In addition, the metal organic frame material improves the interface compatibility between the inorganic nano flame-retardant material and PVC, and further strengthens the mechanical property of the PVC-based wood-plastic composite material.
(2) The in-situ synthesis method can enhance the binding force among the two-dimensional montmorillonite nano-sheets, the transition metal nano-oxides and the metal organic framework material, so that the two-dimensional montmorillonite nano-sheets, the transition metal nano-oxides and the metal organic framework material form a firmly-combined whole. The combination of the two-dimensional montmorillonite nano-sheets, the metal organic frame material and the transition metal nano-oxide can obviously improve the flame retardant property of the PVC-based wood-plastic composite material, and on one hand, the purpose of delaying the volatilization of inflammable gas and the diffusion of oxygen is achieved due to the barrier effect of the two-dimensional montmorillonite nano-sheets. On the other hand, the transition metal nano oxide generates Lewis acid with excellent catalytic char formation effect in the flame retardant process, and the dense carbon layer can prevent further decomposition of the polymer. On the other hand, the metal organic frame material can also increase the carbon addition amount, so that the flame retardant property of the wood-plastic composite material is further improved.
(3) Compared with the existing flame-retardant PVC-based wood-plastic composite material, the inorganic nano-based composite flame retardant in the PVC-based wood-plastic composite material has the advantages of less addition amount, high flame-retardant and smoke-suppressing efficiency, and capability of ensuring the high flame-retardant and smoke-suppressing performance of the PVC-based wood-plastic composite material and simultaneously increasing the mechanical performance of the PVC-based wood-plastic composite material. Moreover, the montmorillonite and the sodium alginate belong to biomass renewable resources, are green, nontoxic and environment-friendly, get rid of dependence on petroleum-based raw materials, and have simple preparation process and easily controlled reaction conditions.
Drawings
FIG. 1 is an SEM image of montmorillonite/ZnO/Cu-MOF of example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
In the description of the present invention, it should be noted that the terms "first," "second," and the like are used for descriptive purposes only and are not indicative or implying relative importance.
Example 1
(1) Adding 0.15g of montmorillonite (average thickness is 80nm, average length is 5 μm) into 100g of deionized water, stirring and ultrasonic treating for 10min, adding 2.5g of sodium alginate, stirring at 70deg.C until completely dissolved, and standing for 14 hr to obtain uniform suspension;
(2) Dropwise adding 20g of the suspension of step (1) to 90gZn (NO) 3 ) 2 ·6H 2 Stirring and crosslinking in O aqueous solution (20 g/L) for 16 hours, filtering to obtain hydrogel spheres with the diameter of 3mm, and washing with deionized water for 2 times;
(3) Drying the hydrogel spheres in the step (2) at 60 ℃ for 25 hours, and calcining at 500 ℃ for 6 hours in an air atmosphere to obtain two-dimensional montmorillonite nano-sheets loaded with transition metal nano-oxides, namely inorganic nano flame-retardant materials;
(4) 12g of inorganic nano flame retardant material, 1g of Cu (NO) 3 ) 2 ·3H 2 Mixing 3g of O, 3g of dimethyl imidazole and 200mL of methanol, stirring at room temperature for self-assembly reaction for 12 hours, centrifuging, washing, and drying at the vacuum of 100 ℃ to obtain the inorganic nano-based composite flame retardant;
(5) Weighing 100g of PVC resin, 40g of poplar powder, 3g of the inorganic nano-based composite flame retardant in the step (4), 2g of a calcium-zinc heat stabilizer, 2g of chlorinated polyethylene and 0.8g of sodium stearate, and mixing in a high-speed mixer to obtain a material;
(6) Extruding the material obtained in the step (5) by a single screw extruder (the barrel temperature is controlled at 162 ℃, the die temperature is 170 ℃, the host rotation speed is 8rpm, and the host current is 16A); finally, hot pressing is carried out for 10min at 155 ℃ and 7MPa by using a hot press, and cooling is carried out until solidification.
FIG. 1 is an SEM image of montmorillonite/ZnO/Cu-MOF of example 1. It can be seen from the figure that the metal organic framework material is coated on the surface of the two-dimensional montmorillonite nano-plate loaded with the transition metal nano-oxide to form a coating layer. The zinc oxide-based inorganic nano-based composite flame retardant comprises a two-dimensional montmorillonite nano-sheet serving as a core and carrying nano ZnO, and a porous coating layer of a metal organic framework material (Cu-MOF) coated on the surface of the core; wherein the average thickness of the two-dimensional montmorillonite nano-sheets in the inner core is 25nm, the average length is 450nm, the particle size of the nano ZnO is 30nm, and the mass ratio of the two-dimensional montmorillonite nano-sheets to the nano ZnO is 0.15:1; the average thickness of the coating layer of Cu-MOF was 5nm.
Example 2
(1) 0.2g of montmorillonite (average thickness 120nm, average length 10 μm) was added to 100g of deionized water, stirred and sonicated for 30min, then 2.0g of sodium alginate was added, stirred at 90℃until completely dissolved, and then left to stand for 24 hours to give a uniform suspension.
(2) Dropwise adding 30g of the suspension obtained in the step (1) to 80g of SnCl 4 ·5H 2 Stirring and crosslinking reaction for 24 hours in O aqueous solution (40 g/L), filtering to obtain hydrogel balls with the diameter of 5mm, and washing with deionized water for 4 times;
(3) Drying the hydrogel spheres in the step (2) at 70 ℃ for 20 hours, and calcining at 600 ℃ for 5 hours in an air atmosphere to obtain two-dimensional montmorillonite nano-sheets loaded with transition metal nano-oxides, namely inorganic nano flame-retardant materials;
(4) 8g of precursor 1, 1gZn (NO 3 ) 2 ·6H 2 Mixing 3g of O, 3g of dimethyl imidazole and 300mL of methanol, stirring at room temperature for self-assembly reaction for 12 hours, centrifuging, washing, and drying at the vacuum of 100 ℃ to obtain the inorganic nano-based composite flame retardant;
(5) Weighing 100g of PVC resin, 45g of poplar powder, 5g of the inorganic nano-based composite flame retardant in the step (4), 8g of barium-zinc heat stabilizer, 4g of polyacrylate and 1.2g of zinc stearate, and mixing in a high-speed mixer to obtain a material;
(6) Extruding the material obtained in the step (5) by a double-screw extruder (the barrel temperature is controlled at 155 ℃, the die temperature is 170 ℃, the host rotation speed is 20rpm, and the host current is 22A); finally, hot pressing is carried out for 15min at 160 ℃ and 8MPa by using a hot press, and cooling is carried out until solidification.
The tin oxide-based inorganic nano-based composite flame retardant comprises load nano SnO serving as a core 2 A porous coating layer of metal organic framework material (Zn-MOF) coated on the surface of the inner core; wherein the average thickness of the two-dimensional montmorillonite nano-sheets in the inner core is 15nm, the average length is 350nm, and the nano SnO is 2 The grain diameter of the nano-meter is 40nm, the two-dimensional montmorillonite nano-sheet and nano SnO 2 The mass ratio of (2) is 0.4:1; the average thickness of the Zn-MOF coating layer was 3nm.
Example 3
(1) Adding 0.15g of montmorillonite (with the average thickness of 100nm and the average length of 8 μm) into 100g of deionized water, stirring and carrying out ultrasonic treatment for 20min, adding 2.0g of sodium alginate, stirring at 80 ℃ until the sodium alginate is completely dissolved, and standing for 20 hours to obtain a uniform suspension;
(2) Dropwise adding 100g of Cu (NO) to 30g of the suspension of step (1) 3 ) 2 ·3H 2 Stirring and crosslinking in O aqueous solution (30 g/L) for 20 hours, filtering to obtain hydrogel spheres with the diameter of 4mm, and washing with deionized water for 3 times;
(3) Drying the hydrogel spheres in the step (2) at 90 ℃ for 20 hours, and calcining the hydrogel spheres at 700 ℃ for 4 hours in an air atmosphere to obtain two-dimensional montmorillonite nano-sheets loaded with transition metal nano-oxides, namely inorganic nano flame-retardant materials;
(4) 10g of inorganic nano flame retardant material, 1gZn (NO 3 ) 2 ·6H 2 Mixing 3g of O, 3g of dimethyl imidazole and 200mL of methanol, stirring at room temperature for self-assembly reaction for 12 hours, centrifuging, washing, and drying at the vacuum of 100 ℃ to obtain the inorganic nano-based composite flame retardant;
(5) Weighing 100g of PVC resin, 30g of poplar powder, 5g of the inorganic nano-based composite flame retardant in the step (4), 6g of a potassium-zinc heat stabilizer, 3g of an ethylene-vinyl acetate copolymer and 0.8g of stearic acid, and mixing in a high-speed mixer to obtain a material;
(6) Extruding the material obtained in the step (5) by a single screw extruder (the barrel temperature is controlled at 160 ℃, the die temperature is 165 ℃, the host rotation speed is 8rpm, and the host current is 20A); finally, hot pressing is carried out for 10min at 160 ℃ and 7MPa by using a hot press, and cooling is carried out until solidification.
The copper oxide-based inorganic nano-based composite flame retardant comprises a two-dimensional montmorillonite nano-sheet serving as a core and carrying nano CuO, and a porous coating layer of a metal organic framework material (Zn-MOF) coated on the surface of the core; wherein the average thickness of the two-dimensional montmorillonite nano-sheets in the inner core is 20nm, the average length is 400nm, the particle size of the nano CuO is 30nm, and the mass ratio of the two-dimensional montmorillonite nano-sheets to the nano CuO is 0.25:1; the average thickness of the Zn-MOF coating layer was 4nm.
Comparative example 1
The preparation of the wood-plastic composite was the same as in example 1, except that no inorganic nano-based composite flame retardant was added.
Comparative example 2
The preparation of the wood-plastic composite is the same as in example 1, except that:
100g of PVC resin, 40g of poplar powder, 0.15g of montmorillonite (average thickness: 100nm, average length: 10 μm), 2.75g of nano ZnO (particle size: 50 nm), 2g of calcium zinc heat stabilizer, 2g of chlorinated polyethylene and 0.8g of sodium stearate are weighed and mixed in a high-speed mixer to obtain a material.
Performance test:
flame retardant and smoke suppression performance: the flame-retardant and smoke-suppressing performance of the PVC-based wood-plastic composite material is detected by adopting a cone calorimeter, and the radiation power is 50Kw/m according to the international standard ISO5660-1-2002 2 The flame retardant and smoke suppression performance test results are shown in table 1;
mechanical properties: the tensile properties were tested according to ASTM D638, with a tensile speed of 5mm/min. The bending performance test was conducted according to ASTM D790, three-point bending mode, span 64mm, load speed 1.9mmm/min, and mechanical properties test results are shown in Table 2.
TABLE 1 flame retardant and smoke suppressant Performance test results
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Ignition time(s) | 108 | 121 | 116 | 25 | 78 |
| Average heat release rate (kW/m) 2 ) | 57.42 | 48.14 | 51.03 | 65.64 | 61.99 |
| Peak heat release rate (kW/m) 2 ) | 109.9 | 101.8 | 105.32 | 117.2 | 113.9 |
| Total heat release (MJ/m) 2 ) | 21.17 | 17.11 | 19.22 | 36.44 | 24.57 |
| Average specific extinction area (m) 2 /kg) | 308.3 | 301.4 | 303.5 | 565.6 | 356.0 |
| Total smoke release (m) 2 ·(kg -1 sample)) | 218.7 | 200.9 | 207.68 | 463.4 | 265.3 |
| Carbon residue ratio (%) | 32.5 | 34.3 | 33.6 | 19.5 | 29.1 |
TABLE 2 mechanical test results
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Tensile Strength/MPa | 34.86 | 35.04 | 34.99 | 28.01 | 27.51 |
| Flexural Strength/MPa | 68.06 | 69.50 | 68.96 | 54.70 | 53.89 |
| Tensile modulus/GPa | 4.32 | 4.38 | 4.26 | 3.73 | 3.59 |
| Flexural modulus/GPa | 3.41 | 3.49 | 3.45 | 3.03 | 2.88 |
| Unnotched impact/kJ/m 2 | 37.97 | 38.12 | 38.08 | 35.19 | 34.24 |
As can be seen from the data results in the table, the inorganic nano-based composite flame retardant prepared by the invention can effectively realize flame retardance and smoke suppression of the PVC-based wood-plastic composite material. As can be seen by comparing the examples with the comparative examples, the ignition time of the PVC-based wood-plastic composite material added with the inorganic nano-based composite flame retardant is greatly improved, on one hand, the probability of fire occurrence is reduced, on the other hand, the escape time is increased when the fire occurs, and meanwhile, the heat release of the PVC-based wood-plastic composite material added with the inorganic nano-based composite flame retardant is obviously reduced, and the flame retardant effect is obvious; the smoke release parameters, such as the average extinction area and the total smoke release, are greatly reduced, so that the PVC-based wood-plastic composite material prepared by the invention has excellent smoke suppression performance. As can be seen from the mechanical property test results in Table 2, the inorganic nano-based composite flame retardant prepared by the invention can improve the mechanical property of the PVC-based wood-plastic composite material.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (20)
1. An inorganic nano-based composite flame retardant, wherein the inorganic nano-based composite flame retardant comprises a transition metal nano-oxide, a two-dimensional montmorillonite nano-sheet and a metal organic framework material; the transition metal nano-oxide is loaded on the surface of the two-dimensional montmorillonite nano-sheet to form the two-dimensional montmorillonite nano-sheet loaded with the transition metal nano-oxide; the metal organic frame material is coated on the surface of the two-dimensional montmorillonite nano-sheet loaded with the transition metal nano-oxide to form a coating layer;
the transition metal nano oxide is at least one selected from nano zinc oxide, nano tin oxide, nano chromium oxide, nano iron oxide, nano cobalt oxide, nano nickel oxide and nano copper oxide;
the metal organic framework material is selected from at least one of Zn-MOF, fe-MOF, cu-MOF, sn-MOF, co-MOF, ni-MOF and Cr-MOF;
the organic ligand forming the metal organic framework material is selected from at least one of 2-amino terephthalic acid, dimethyl imidazole, 2, 5-dihydroxyterephthalic acid, trimesic acid or terephthalic acid;
the transition metal salt forming the metal organic framework material is selected from at least one of zinc salt, tin salt, chromium salt, ferric salt, cobalt salt, nickel salt and copper salt.
2. The inorganic nano-based composite flame retardant according to claim 1, wherein the particle size of the transition metal nano-oxide is 20nm to 80nm;
and/or the average thickness of the two-dimensional montmorillonite nano-sheets is 10 nm-30 nm; the average length of the two-dimensional montmorillonite nano-sheets is 300 nm-500 nm.
3. The inorganic nano-based composite flame retardant according to claim 1, wherein the transition metal salt forming the metal organic framework material is selected from at least one of zinc nitrate, tin chloride, chromium nitrate, iron nitrate, cobalt nitrate, nickel nitrate, copper nitrate;
and/or the mass ratio of the transition metal salt forming the metal organic framework material and the organic ligand forming the metal organic framework material is 1 (2-4).
4. The inorganic nano-based composite flame retardant according to claim 1, wherein the mass ratio of the two-dimensional montmorillonite nano-sheets to the transition metal nano-oxide is (0.1-0.5): 1;
and/or the average thickness of the coating layer is 3 nm-6 nm;
and/or the mass of the metal organic framework material accounts for 0.5-3 wt% of the total mass of the inorganic nano-based composite flame retardant.
5. A method for preparing the inorganic nano-based composite flame retardant according to any one of claims 1 to 4, comprising the steps of:
(1) Mixing montmorillonite and sodium alginate to prepare a suspension;
(2) Dropwise adding the suspension in the step (1) into the aqueous solution of the first transition metal salt, and performing a crosslinking reaction to prepare hydrogel spheres;
(3) Drying the hydrogel spheres in the step (2) and calcining to prepare two-dimensional montmorillonite nano-sheets loaded with transition metal nano-oxides;
(4) Mixing the two-dimensional montmorillonite nano-sheets loaded with the transition metal nano-oxides, the second transition metal salt, the organic ligand and the organic solvent in the step (3), and performing self-assembly reaction to prepare the inorganic nano-based composite flame retardant.
6. The method for preparing an inorganic nano-based composite flame retardant according to claim 5, wherein in the step (1), the montmorillonite has a lamellar structure, the average thickness of montmorillonite lamellar is 80nm to 120nm, and the average length of montmorillonite lamellar is 5 μm to 10 μm;
and/or in the step (1), the mass ratio of the montmorillonite to the sodium alginate is (0.01-0.1): 1.
7. The method for preparing an inorganic nano-based composite flame retardant according to claim 5, wherein in the step (2), the first transition metal salt is at least one selected from zinc salt, tin salt, chromium salt, iron salt, cobalt salt, nickel salt and copper salt;
and/or, in the step (2), the concentration of the transition metal salt in the aqueous solution of the first transition metal salt is 10-50g/L;
and/or, in the step (2), the mass ratio of the suspension to the aqueous solution of the first transition metal salt is (10-50): 100;
and/or in the step (2), the temperature of the crosslinking reaction is room temperature, and the time of the crosslinking reaction is 16-28 hours.
8. The method for preparing an inorganic nano-based composite flame retardant according to claim 7, wherein the first transition metal salt is at least one selected from zinc nitrate, tin chloride, chromium nitrate, iron nitrate, cobalt nitrate, nickel nitrate, and copper nitrate.
9. The method for preparing an inorganic nano-based composite flame retardant according to claim 5, wherein in the step (3), the calcination temperature is 400-800 ℃, the calcination time is 2-6 hours, and the calcination atmosphere is an air atmosphere.
10. The method for preparing an inorganic nano-based composite flame retardant according to claim 5, wherein in the step (4), the organic ligand is selected from at least one of 2-amino terephthalic acid, dimethylimidazole, 2, 5-dihydroxyterephthalic acid, trimesic acid and terephthalic acid;
and/or, in the step (4), the second transition metal salt is selected from at least one of zinc salt, tin salt, chromium salt, iron salt, cobalt salt, nickel salt and copper salt;
and/or, in the step (4), the mass ratio of the second transition metal salt to the organic ligand is 1 (2-4);
and/or, in the step (4), the volume ratio of the sum of the masses of the second transition metal salt and the organic ligand to the organic solvent is (0.01-0.05) g/1 mL;
and/or in the step (4), the mass ratio of the second transition metal salt to the two-dimensional montmorillonite nano-sheet loaded with the transition metal nano-oxide is 1 (5-15);
and/or, in the step (4), the temperature of the self-assembly reaction is 25-80 ℃; the self-assembly reaction time is 6-24 h.
11. The method for preparing an inorganic nano-based composite flame retardant according to claim 10, wherein the second transition metal salt is at least one selected from zinc nitrate, tin chloride, chromium nitrate, iron nitrate, cobalt nitrate, nickel nitrate, copper nitrate.
12. Use of the inorganic nano-based composite flame retardant according to any one of claims 1-4 in wood-plastic composites.
13. The use according to claim 12, wherein the wood-plastic composite is a PVC-based wood-plastic composite.
14. A wood-plastic composite, wherein the wood-plastic composite comprises the inorganic nano-based composite flame retardant of any one of claims 1-4.
15. The wood-plastic composite of claim 14, wherein the wood-plastic composite further comprises a PVC resin, a plant fiber powder, an impact modifier, a lubricant, and optionally a heat stabilizer.
16. The wood-plastic composite according to claim 15, wherein the wood-plastic composite comprises the following components in mass fraction:
100 parts by mass of PVC resin;
30-60 parts of plant fiber powder;
1-10 parts by mass of an inorganic nano-based composite flame retardant;
0-6 parts by mass of a heat stabilizer;
2-4 parts by mass of an impact modifier;
0.8-1.2 parts by mass of lubricant.
17. The wood-plastic composite according to claim 15, wherein the plant fiber powder is selected from at least one of poplar powder, bamboo powder, crop straw powder, and fruit shell powder.
18. A method of preparing a wood-plastic composite according to any one of claims 14 to 17, the method comprising the steps of:
(a) Respectively weighing PVC resin, plant fiber powder, inorganic nano-based composite flame retardant, heat stabilizer, impact modifier and lubricant according to the parts by mass, and mixing to obtain materials;
(b) And (c) extruding the material obtained in the step (a) through a screw extruder for molding, and then performing hot pressing and curing to obtain the wood-plastic composite material.
19. The process according to claim 18, wherein in the step (b), the temperature of the processing zone is 140 to 180℃and the die temperature is 150 to 170℃during the extrusion.
20. The production method according to claim 18, wherein in the step (b), the hot press is used for hot pressing at 155 to 175 ℃ under a pressure of 7MPa for 10 to 20 minutes.
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| CN106519496A (en) * | 2016-11-02 | 2017-03-22 | 华北科技学院 | Compound PVC flame retardant, flame-resistant material and preparation method |
| CN109663576A (en) * | 2019-02-02 | 2019-04-23 | 西北师范大学 | A kind of montmorillonite load molysite MOFs adsorbent and preparation method thereof |
| CN110105583A (en) * | 2019-05-08 | 2019-08-09 | 中国科学技术大学 | A kind of metal oxide/ZIF composite material, preparation method and application |
| CN114680133A (en) * | 2022-03-18 | 2022-07-01 | 湖南工业大学 | Metal organic framework/montmorillonite composite material and preparation method and application thereof |
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| CN106519496A (en) * | 2016-11-02 | 2017-03-22 | 华北科技学院 | Compound PVC flame retardant, flame-resistant material and preparation method |
| CN109663576A (en) * | 2019-02-02 | 2019-04-23 | 西北师范大学 | A kind of montmorillonite load molysite MOFs adsorbent and preparation method thereof |
| CN110105583A (en) * | 2019-05-08 | 2019-08-09 | 中国科学技术大学 | A kind of metal oxide/ZIF composite material, preparation method and application |
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